Water repellent textile material



Patented Feb. 27, 1940 UNITED STATES PATENT orl-"lcc I 2,191,982 WATER REPELLENT TEXTILE MATERIAL No Drawing. Application July 12, 1938, Serial No. 218,800. In Germany July 26, 1937 12 Claims.

The present invention relates to a process for rendering fibrous materials water-repellent, and to materials so treated.

The known processes for making fibrous materials, especially textiles, water-repellent or impervious to water have the disadvantage that the effects so obtained are not sufiiciently fast to wet treatments so that the materials lose their water-repellent properties, for instance, by dyeing, washing or like wet treatments. We have now found that water-repellent properties of very good fastness to wet treatments can be imparted to any kind of textile material by treating the materials with an organic compound containing a complex forming group and a hydrophobe radical and with a soluble complex forming metal compound selected from the group consisting of chromium compounds and zirconium compounds.

We have, furthermore, found that such organic compounds are especially useful for the purpose of our invention as contain, attached to an aromatic nucleus in o-position to each other, a hydroxy or mercapto group and a carboxylic acid group, i. e. compounds like salicylic acid, thiosalicylic acid and derivatives thereof. The compounds to be used for our invention should, furthermore, preferably contain as a hydrophobe radical, an aliphatic radical of at least 10 carbon atoms directly connected with each other which may be attached to the salicylic acid grouping directly or by means of a hetero atom or a hetero atom group. Compounds of this kind which may be employed for the purpose of our invention,

are, for instance, the following:

Stearoyl-p-aminosalicylic acid Isoheptoyl-p-aminosalicylic acid Lauroyl-p-aminosalicylic acid StearoyF-p-aminothiosalicylic acid 55 4-hydroxydiphenyl-3-carboxylic acid The alkylation product of 2.3-hydroxynaphthoic acid with dodecylene The condensation product of isooctylphenol-ocarboxylic acid with formaldehyde Reaction products of polyethylene-diamines and/or -imines with chloromethylcresotic acid Reaction product of salicylic acid-disulfochloride with 2 mol dodecylamine 10 Among the soluble compounds of zirconium those are especially suitable which dissolve in water with strong acid reaction, like zirconium chloride, zirconium nitrate and the water-soluble hydrolysates obtainable therefrom.

Our present process is preferably performed by impregnating the fibrous material with a solution of the organic component and, either before or afterwards, with a solution of the metal compound. In the case of artificial fibrous material go it is also possible to incorporate with spinning solutions thereof a difllcultly soluble organic compound, containing, for instance, the salicylic acid grouping, and to aftertreat the material so obtained with a solution of the metal compound. Our new process may be combined with other textile treatment processes, for instance, with animalizing of artificial fibers or with the dyeing of wool with such dyestuffs which are chromed on the fiber (use of chromium compounds). It may be noted, however, that the best result so far has been obtained by using zirconium compounds.

Example 1 A staple fiber fabric from viscose is treated 35 for 1 minute at 90 C. with an aqueous solution of 10 g. /l. of a sodium salt of stearyl-p-aminosalicylic acid, hydroextracted and dried for a short time. Thereupon the material is immersed for 5 minutes at 90 C. in an aqueous solution of 2,5 g./l. zirconiumoxychloride and 1 g./l. crystallized sodium acetate again hydroextracted and dried at 95-100 C.for 20 minutes. The fabric is waterrepellent and does not lose this property by washing with soap even if it is boiled for 10 minutes with an aqueous solution of 5 g./l. Marsellle soap and 3 g./l. soda.

Instead of the sodium salt of stearyl-p-aminosalicylic acid there may be used with similar result, for instance, the sodium salts of lauroylor isoheptoyl-p-aminosalicylic acid or the urea derivative which is obtainable from p-aminosalicylic acid and octadecylisocyanate. In a similar way the above mentioned organic compounds may be used. The materials treated in this man- 55 ner, besides being water-repellent, display an agreeable full handle.

Example 2 A staple fiber fabric from viscose is treated for 2 minutes at 90 C. with an aqueous solution of 10 g./l. zirconiumoxychloride and 4 g./l. crystallized sodium acetate. After hydroextraction and a short drying the fabric is treated for 2 minutes at 90 C. with an aqueous solution of 10 g./l. of the sodium salt of stearylureido-salicyclic acid, again hydroextracted and dried. The fabric has become water-repellent arid does not appreciably lose this property after washing and drying.

Example 3 Example 4 The process as described in Example 3 may be applied with similar results to staple fiber fabrics which have been dyed with substantive dyestuffs, or to mixed fabrics from 1 part staple fiber and 1 part cotton or wool, or to satin-twill, wool fiannels or animalized copper artificial silk.

Example 5 A staple fiber fabric from viscose is treated as described in Example 1 with a sodium salt of stearoyl-p-aminosalieylic acid rnd thereupon,

with an aqueous solution of 15 g./l. of a B. solution of chromium acetate for 1 minute at 90 C. The fabric is then hydroextracted and dried for 30 minutes at 30 C. The fabric has become water-repellent; the impregnation is fast to washing and boiling. Instead of the p-aminosalicylic acid compound the other above mentioned compounds may be used.

Example 6 A staple fiber fabric from viscose is treated with a hot aqueous solution of 10 g./l. of the sodium salt of stearoyl-p-aminosalicylic acid, squeezed and thereupon treated for some minutes at 90 C. with an aqueous solution of 5 g./l. crystallized zirconiumoxychloride (having a zirconium content corresponding to about 44% ZrOz) and 2 g./l. crystallized sodium acetate. The fabric is again squeezed and immersed for a short time into an aqueous solution of 10 g./l. crystallized sodium acetate. After hydroextracting and drying at 110 C. the fabric has become water-repellent and does not lose this property even on Washing and boiling.

Example 7 A staple fiber fabric from viscose is impregnated with an aqueous solution of 1C g./l. of the sodium salt of technical alkyl salicylic acid (alkyl denotingalkyl radicals of from 10-18 carbon atoms). Thereupon the fabric is treated for some minutes with an aqueous solution of zirconiumoxychloride and sodium acetate as described in the foregoing example. After squeezing the fabric is treated for a short time in an aqueous solution of crystallized sodium acetate,

hydroextracted and dried at 80-100 C. The fabric is water-repellent and does not lose this property even on washing, boiling and fulling. Instead of the zirconiumoxychloride also 20 com. of the zirconiumhydroxide sol containing about I 9.4% ZlOz and being obtainable, for instance,

corresponding to Example 4 of the German specification 582,682 may be employed.

Eaample 8 effect is fast to washing. It is practically not impaired by boiling with an aqueous solution of 5 g./l. Marseille soap and 3 g./l. soda, or by fulling in an aqueous bath containing 50 g./l. soap and 5 g./l. soda or by treating with benzine or boiling for some hours in carbon tetrachloride.

Example 9 Instead of the zirconiumoxychloride of Example 1 6.5 g./l. zirconiumnitrate per liter water containing, besides, 2 g;/l. crystallized sodium acetate may be used. After the zirconiumnitrate treatment the fabric is hydroextracted, rinsed for a short time with cold water and dried at 100 C. The result is similar as obtained according to Example 1.

Example '10 A cellulose acetate artificial silk fabric is treated for 10 minutes at 70 C. with a 1% aqueous solution of the sodium salt of stearoylp-aminosalicylic acid, slightly squeezed and dried. Thereupon the fabric is immersed for 5 minutes into a 2% aqueous solution of zirconium acetate or zirconium formate. After squeezing again the fabric is dried at 90-100" C. The fabric is excellently water-repellent.

Example 11 A staple fiber fabric from viscose is impregnated at C., with a solution of the sodium salt of stearoyl-p-aminosalicylic acid, hydroextracted and dried. Thereupon it is treated for a short time with a cold solution of 24 g./l. zirconiumoxychloride (containing 46% ZIO2) and 16 g./l.

crystallized sodium acetate or 12 g./l. sodium tetraborate. After squeeezing and drying for 40 minutes at 90-95 C. the fabric has become water-repellent and does not lose this property even on washing and boiling.

We claim:

1. Process of rendering textile material waterrepellent which comprises treating the material with an aromatic orthohydroxy carboxylic acid compound containing a hydrophobe radical, and with a water soluble complex forming metal compound selected from the group consisting of chr0- mium compounds and zirconium compounds.

2. Process of rendering textile material waterrepellent which comprises treating the material with an aromatic orthohydroxy carboxylic acid compound containing an aliphatic hydrocarbon radical of at least 10 carbon atoms directly connected with each other, and with a water soluble zirconium compound.

3. Process of rendering textile material water-repellent which comprises treating the material with an aromatic orthohydroxy carboxylic acid compound containing an aliphatic hydrocarbon radical corresponding to the radicals of the naturalhigher fatty acids, and with a water soluble zirconium compound.

4. Process of rendering textile material waterrepellent which comprises treating the material with a salicylic acid compound containing an aliphatic radical corresponding to the hydrocarbon radicals of the natural higher fatty acids, and with a water soluble zirconium compound.

5. Process of rendering textile material waterrepellent which comprises treating the material with an aromatic orthohydroxy carboxylic acid compound containing an aliphatic hydrocarbon radical corresponding to the radicals of the natural higher fatty acids and with a zirconium compound being soluble with strong acid reaction-in water and being selected from the group consisting of zirconium chloride, zirconium nitrate and I the water soluble hydrolysates obtainable therefrom. Y

6. Process of rendering textile material waterrepellent which comprises treating the material with a salicylic acid compound containing an ali phatic hydrocarbon radical corresponding tothe radicals of the natural higher fatty acids and with a zirconium compound being soluble with strong acid reaction in water and being selected from the group consisting of zirconium chloride, zirconium nitrate and the water soluble hydrolysates obtainable therefrom.

7. Textile material when treated according to the process of claim 1.

8. Textile material when treated according to the process of claim 2.

9. Textile material when treated according to the process of claim 3.

10. Textile material when treated according to the process of claim 4.

11. Textile material when treated according to the process of claim 5.

12. Textile material when treated according to the process of claim 6.

ARNOLD DOSER. o'rro BAYER. KARL muzumm. 

